GaSe and Ga2Se3 are semiconducting compounds formed from same constituent elements. These compounds have been attractive due to their optoelectronic and photovoltaic applications. Defects take remarkable attention since they affect quality of semiconductor devices. In the present paper, deep defect centers in GaSe and Ga2Se3 single crystals grown by Bridgman method were reported from the analyses of thermoluminescence measurements performed in the 350-675 K range. Experimental TL curves of GaSe and Ga2Se3 single crystals presented one and two overlapped peaks, respectively. The applied curve fitting and initial rise techniques were in good agreement about trap activation energies of 0.83 eV for GaSe, 0.96 and 1.24 eV for Ga2Se3 crystals. Crystalline structural properties of the grown single crystals were also investigated by x-ray diffraction measurements. The peaks observed in XRD patterns of the GaSe and Ga2Se3 crystals were well-consistent with hexagonal and zinc blende structures, respectively.